WO2020122371A1 - Polyolefin and method for preparing same - Google Patents

Abstract

A polyolefin and a method for preparing same are provided. The polyolefin is formed by copolymerizing an olefin-based monomer and a comonomer in the presence of an olefin polymerization catalyst comprising a transition metal compound for an olefin polymerization catalyst represented by formula 1, and the weight average molecular weight (Mw) thereof may be 20,000 or less. The description of formula 1 is the same as that in the description of the invention.

Description

Polyolefin and its manufacturing method

The present invention relates to a polyolefin and a method for producing the same, and more particularly, to a polyolefin having a low molecular weight and low viscosity properties using a transition metal compound for an olefin polymerization catalyst and a method for manufacturing the same.

Metallocene catalyst, which is one of the catalysts used to polymerize olefins, is a compound in which a ligand such as a cyclopentadienyl group, an indenyl group, or a cycloheptadienyl group is coordinated to a transition metal or a transition metal halogen compound. Have

The metallocene catalyst is a single-site catalyst composed of the metallocene compound and a co-catalyst such as methylaluminoxane. The polymer polymerized with the metallocene catalyst has a narrow molecular weight distribution and a pore size. The monomer distribution is uniform, and the copolymerization activity is higher than that of the Ziegler-Natta catalyst.

However, since there are still many difficulties in commercial use, a manufacturing technique based on development and economic efficiency of a catalyst having high stability or excellent reactivity with olefin is required even at high temperatures.

The problem to be solved by the present invention is an olefin polymerization catalyst having a high stability even at high temperature and an excellent reactivity with an olefin, including a transition metal compound for an olefin polymerization catalyst, and polymerization using the same to obtain excellent physical properties such as low molecular weight and low viscosity. It is to provide the polyolefin which has.

The problems of the present invention are not limited to the technical problems mentioned above, and other technical problems not mentioned will be clearly understood by those skilled in the art from the following description.

The polyolefin according to one embodiment for solving the above problems is formed by copolymerization of an olefinic monomer and a comonomer under an olefin polymerization catalyst including a transition metal compound for an olefin polymerization catalyst represented by the following Chemical Formula 1, and a weight average molecular weight (Weight The average molecular weight (Mw) may be 20,000 or less.

<Formula 1>

(In the formula 1, M is titanium (Ti), zirconium (Zr) or hafnium (Hf), X are each independently halogen, C _1-20 alkyl, C _2-20 alkenyl, C _2-20 alkynyl , C _6-20 aryl, C _1-20 alkyl C _6-20 aryl, C _6-20 aryl C _1-20 alkyl, C _1-20 alkylamido, C _6-20 arylamido or C _1-20 alkyl Ridene, R ¹ to R ⁴ are each independently hydrogen, C _1-20 alkyl, C _2-20 alkenyl, C _2-20 alkynyl, C _6-20 aryl, C _1-20 alkyl C _6-20 aryl , C _6-20 aryl C _1-20 alkyl, C _1-20 alkylamido, C _6-20 arylamido or C _1-20 alkylidene, R ⁵ and R ⁶ are each independently C _1-20 alkyl , C _2-20 alkenyl, C _2-20 alkynyl, C _6-20 aryl, C _1-20 alkyl C _6-20 aryl, C _6-20 aryl C _1-20 alkyl, C _1-20 alkylamido , C _6-20 arylamido or C _1-20 alkylidene, or are connected to each other to form a substituted or unsubstituted C _4-20 ring, and R ⁷ to R ¹⁰ are connected or substituted by two neighboring two groups Form a substituted C _4-20 ring)

The polyolefin may have a viscosity measured at 177°C of 5000 cP to 10000 cP.

The polyolefin may have a number average molecular weight (Mn) of 10,000 or less, and a molecular weight distribution (MWD) defined by the following Equation 1 may range from 2 to 3.

[Equation 1]

Mw/Mn

The olefinic monomer may be ethylene, and the co-monomer may be 1-octene.

X is each independently halogen or C _1-20 alkyl, R ¹ , R ³ , and R ⁴ are each hydrogen, R ² is C _1-20 alkyl, and R ⁵ and R ⁶ are each independently As C _1-20 Alkyl or C _6-20 Aryl, or connected to each other to form a substituted or unsubstituted aliphatic C _4-20 ring, the R ⁷ to R ¹⁰ are two adjacent to each other are connected to each other to be substituted or unsubstituted Aromatic C _5-20 ring.

The R ⁵ and R ⁶ are each independently methyl (methyl), or may be connected to each other to form an aliphatic C ₄ ring.

The R ⁷ to R ¹⁰ may be connected to two adjacent ones to form a substituted or unsubstituted aromatic C ₆ .

The Chemical Formula 1 may be at least one of the following Chemical Formulas 1-1 to 1-12.

<Formula 1-1>

<Formula 1-2>

<Formula 1-3>

<Formula 1-4>

<Formula 1-5>

<Formula 1-6>

<Formula 1-7>

<Formula 1-8>

<Formula 1-9>

<Formula 1-10>

<Formula 1-11>

<Formula 1-12>

(In the formulas 1-1 to 1-12, M is zirconium or hafnium, and X is each independently halogen or C _1-20 alkyl)

The Chemical Formula 1 may be at least one of the following Chemical Formulas A to D.

<Formula A>

<Formula B>

<Formula C>

<Formula D>

The method for producing a polyolefin according to an embodiment for solving the above problems includes forming a polyolefin by polymerizing an olefin-based monomer and a comonomer under an olefin polymerization catalyst including a transition metal compound represented by the following Chemical Formula 1 Can be.

<Formula 1>

(In the formula 1, M is titanium (Ti), zirconium (Zr) or hafnium (Hf), X are each independently halogen, C _1-20 alkyl, C _2-20 alkenyl, C _2-20 alkynyl , C _6-20 aryl, C _1-20 alkyl C _6-20 aryl, C _6-20 aryl C _1-20 alkyl, C _1-20 alkylamido, C _6-20 arylamido or C _1-20 alkyl Ridene, R ¹ to R ⁴ are each independently hydrogen, C _1-20 alkyl, C _2-20 alkenyl, C _2-20 alkynyl, C _6-20 aryl, C _1-20 alkyl C _6-20 aryl , C _6-20 aryl C _1-20 alkyl, C _1-20 alkylamido, C _6-20 arylamido or C _1-20 alkylidene, R ⁵ and R ⁶ are each independently C _1-20 alkyl , C _2-20 alkenyl, C _2-20 alkynyl, C _6-20 aryl, C _1-20 alkyl C _6-20 aryl, C _6-20 aryl C _1-20 alkyl, C _1-20 alkylamido , C _6-20 arylamido or C _1-20 alkylidene, or are connected to each other to form a substituted or unsubstituted C _4-20 ring, and R ⁷ to R ¹⁰ are connected or substituted by two neighboring two groups Form a substituted C _4-20 ring)

The Chemical Formula 1 may be at least one of the following Chemical Formulas 1-1 to 1-12.

<Formula 1-1>

<Formula 1-2>

<Formula 1-3>

<Formula 1-4>

<Formula 1-5>

<Formula 1-6>

<Formula 1-7>

<Formula 1-8>

<Formula 1-9>

<Formula 1-10>

<Formula 1-11>

<Formula 1-12>

(In the formulas 1-1 to 1-12, M is zirconium or hafnium, and X is each independently halogen or C _1-20 alkyl)

The Chemical Formula 1 may be at least one of the following Chemical Formulas A to D.

<Formula A>

<Formula B>

<Formula C>

<Formula D>

The olefin polymerization catalyst may have a catalytic activity ranging from 160 kg-PE/g-Cat to 200 kg-PE/g-Cat.

The polyolefin may have a weight average molecular weight (Mw) of 20,000 or less.

The polyolefin may have a viscosity measured at 177°C of 5000 cP to 10000 cP.

The polyolefin may have a number average molecular weight (Mn) of 10,000 or less, and a molecular weight distribution (MWD) defined by the following Equation 1 may range from 2 to 3.

[Equation 1]

Mw/Mn

The olefinic monomer may be ethylene, and the comonomer may be 1-octene.

The olefin polymerization catalyst may further include a cocatalyst compound.

The cocatalyst compound may include at least one of a compound represented by the following formula (I), a compound represented by the formula (II), and a compound represented by the formula (III).

<Formula Ⅰ>

(In Formula A, n is an integer of 2 or more, and R _a is a halogen atom, a C _1-20 hydrocarbon group, or a C _1-20 hydrocarbon group substituted with halogen)

<Formula Ⅱ>

(In the formula B, D is aluminum (Al) or boron (B), and R _b , R _c and R _d are each independently a halogen atom, a C _1-20 hydrocarbon group, or a C _1-20 hydrocarbon group substituted with halogen. Or a C _1-20 alkoxy group)

<Formula Ⅲ>

^{[LH] + [Z (A} ) 4] - or ^{[L] + [Z (A} ) 4] -

(In the formula C, L is a neutral or cationic Lewis base, [LH] ⁺ and [L] ⁺ are Brønsted acids, Z is a group 13 element, and A is each independently substituted or unsubstituted C _{6- 20} aryl group or a substituted or unsubstituted C _1-20 alkyl group)

Details of other embodiments are included in the detailed description and drawings.

The polyolefin polymerized using the olefin polymerization catalyst that has high stability at high temperature and reacts with the olefin, including the transition metal compound of the present invention, may have excellent properties such as low molecular weight and low viscosity.

In addition, the olefin polymerization catalyst comprising the transition metal compound of the present invention has a high synthetic yield and can be easily produced by an economical method, and thus has excellent commercial practicality.

The effects according to the embodiments of the present invention are not limited by the contents exemplified above, and more various effects are included in the present specification.

Advantages and features of the present invention, and methods for achieving them will be clarified with reference to embodiments described below in detail together with the accompanying drawings. However, the present invention is not limited to the embodiments disclosed below, but will be implemented in various different forms, and only the embodiments allow the disclosure of the present invention to be complete, and the ordinary knowledge in the technical field to which the present invention pertains. It is provided to fully inform the holder of the scope of the invention, and the invention is only defined by the scope of the claims.

In the present specification, the term "C _AB "means "carbon number A or more and B or less", and the term "A to B" means "A or more and B or less" and the term "substituted or unsubstituted""Substitutedfrom" means "at least one hydrogen of a hydrocarbon compound or hydrocarbon derivative is halogen, C _1-20 alkyl, C _2-20 alkenyl, C _2-20 alkynyl, C _6-20 aryl, C _1- Means substituted with ₂₀ alkyl C _6-20 aryl, C _6-20 aryl C _1-20 alkyl, C _1-20 alkylamido, C _6-20 arylamido or C _1-20 alkylidene," “Unsubstituted” means “at least one hydrogen of a hydrocarbon compound or hydrocarbon derivative is halogen, C _1-20 alkyl, C _2-20 alkenyl, C _2-20 alkynyl, C _6-20 aryl, C _1-20 alkyl C _6-20 aryl, C _6-20 aryl C _1-20 alkyl, C _1-20 alkylamido, C _6-20 arylamido or C _1-20 alkylidene.

The polyolefin according to an embodiment of the present invention may be formed by copolymerizing an olefinic monomer and a comonomer.

Polyolefins are homopolymers or copolymers polymerized by polymerization reaction such as free radical, cationic, coordination, condensation, and addition. ), but is not limited thereto.

In an exemplary embodiment, the polyolefin may be prepared by gas phase polymerization, solution polymerization or slurry polymerization. Examples of the solvent that can be used when the polyolefin is prepared by solution polymerization or slurry polymerization include C _5-12 aliphatic hydrocarbon solvents such as pentane, hexane, heptane, nonane, decane and isomers thereof; Aromatic hydrocarbon solvents such as toluene and benzene; Hydrocarbon solvents substituted with chlorine atoms such as dichloromethane and chlorobenzene; Although a mixture of these etc. are mentioned, it is not limited to these.

The olefinic monomers are C _2-20 alpha-olefin, C _1-20 diolefin, C _3-20 cyclo-olefin and C _3-20 cyclodiolefin. It may be one or more selected from the group consisting of.

In an exemplary embodiment, the olefinic monomer is ethylene, propylene, 1-butene, 1-pentene, 4-methyl-1-pentene, 1-hexene, 1-heptene, 1-octene, 1-decene, 1-undecene , 1-dodecene, 1-tetradecene, 1-hexadecene, and the like, and the polyolefin may be a homopolymer containing only one olefin-based monomer exemplified above, or a copolymer containing two or more kinds.

Preferably, the polyolefin may be a copolymer of ethylene and 1-octene, but is not limited thereto.

The polyolefin according to an embodiment of the present invention may have a weight average molecular weight (Mw) of 20,000 or less.

The polyolefin is polymerized under a catalyst containing a transition metal compound for an olefin polymerization catalyst, which will be described later, and may have low molecular weight and low viscosity properties compared to the same olefin polymer. The transition metal compound has a high catalytic activity with respect to the olefinic monomer, and can polymerize a low molecular weight polyolefin even when a relatively small amount of hydrogen (H ₂ ) is injected. The polyolefin according to an embodiment of the present invention has a low molecular weight and thus exhibits low viscosity, and accordingly, the polyolefin may be used as a raw material for a wax or adhesive.

According to an embodiment of the present invention, the polyolefin may have a viscosity measured at 177°C of 5000 cP to 10000 cP. A detailed description of this will be described later with reference to the experimental example.

In addition, according to one embodiment of the present invention, the polyolefin may have a number average molecular weight (Mn) of 10,000 or less, and a molecular weight distribution (MWD) defined by Equation 1 below It may have a range of 2 to 3.

[Equation 1]

MWD = Mw/Mn

Meanwhile, as described above, the polyolefin of the present invention may be formed by polymerizing an olefinic monomer under an olefin polymerization catalyst.

The polyolefin according to an embodiment of the present invention may be polymerized under an olefin polymerization catalyst including a transition metal compound for an olefin polymerization catalyst represented by Chemical Formula 1 below.

<Formula 1>

In Chemical Formula 1, M may be titanium (Ti), zirconium (Zr), or hafnium (Hf). Specifically, M may be zirconium or hafnium.

X is each independently halogen, C _1-20 alkyl, C _2-20 alkenyl, C _2-20 alkynyl, C _6-20 aryl, C _1-20 alkyl C _6-20 aryl, C _6-20 aryl C _1-20 alkyl, C _1-20 alkylamido, C _6-20 arylamido or C _1-20 alkylidene. Specifically, X may be each independently halogen or C _1-20 alkyl. More specifically, X may be each independently chlorine (Cl) or methyl (methyl).

R ¹ to R ⁴ are each independently hydrogen, C _1-20 alkyl, C _2-20 alkenyl, C _2-20 alkynyl, C _6-20 aryl, C _1-20 alkyl C _6-20 aryl, C _{6 -20} aryl C _1-20 alkyl, C _1-20 alkylamido, C _6-20 arylamido or C _1-20 alkylidene. Specifically, R ¹ , R ³ and R ⁴ are each hydrogen, and R ² may be C _1-20 alkyl. More specifically, R ¹ , R ³ and R ⁴ are each hydrogen, and R ² may be n-butyl.

R ⁵ and R ⁶ are each independently C _1-20 alkyl, C _2-20 alkenyl, C _2-20 alkynyl, C _6-20 aryl, C _1-20 alkyl C _6-20 aryl, C _6-20 Aryl C _1-20 alkyl, C _1-20 alkylamido, C _6-20 arylamido or C _1-20 alkylidene, or may be linked to each other to form a substituted or unsubstituted C _4-20 ring. Specifically, R ⁵ and R ⁶ are each independently C _1-20 alkyl or C _6-20 aryl, or may be connected to each other to form a substituted or unsubstituted aliphatic C _4-20 ring. More specifically, R ⁵ and R ⁶ are each independently methyl, or may be connected to each other to form an aliphatic C ₄ ring.

R ⁷ to R ¹⁰ may be connected to two neighboring groups to form a substituted or unsubstituted C _4-20 ring. Specifically, R ⁷ to R ¹⁰ may be connected to two neighboring groups to form a substituted or unsubstituted aromatic C _5-20 ring. More specifically, R ⁷ to R ¹⁰ may be connected to two neighboring groups to form a substituted or unsubstituted aromatic C ₆ ring. Two neighboring R ⁷ to R ¹⁰ may mean R ⁷ and R ⁸ or R ⁹ and R ¹⁰ .

The aromatic C ₆ ring may be substituted with one or more of halogen, C _6-20 aryl, C _1-20 alkylsilyl, C _1-20 alkyloxy and C _1-20 alkylamino. have. Specifically, the halogen is fluorine (F), the C _6-20 aryl is phenyl, the C _1-20 alkylsilyl is trimethylsilyl (-SiMe ₃ ), and the C _1-20 alkyloxy is methyl Oxy(methyloxy[methoxy], -OMe), and the C _1-20 alkylamino may be dimethylamino (-NMe ₂ ).

Specifically, the transition metal compound may be represented by at least one of the following Chemical Formulas 1-1 to 1-12.

<Formula 1-1>

<Formula 1-2>

<Formula 1-3>

<Formula 1-4>

<Formula 1-5>

<Formula 1-6>

<Formula 1-7>

<Formula 1-8>

<Formula 1-9>

<Formula 1-10>

<Formula 1-11>

<Formula 1-12>

In Formulas 1-1 to 1-12, M is zirconium or hafnium, and X may be each independently halogen or C _1-20 alkyl.

In an exemplary embodiment, the transition metal compound may be any one or more of the following Formulas A to D.

<Formula A>

<Formula B>

<Formula C>

<Formula D>

Preferably, the transition metal compound may be a compound of Formula A. Formula A by containing hafnium (Hf) as the central metal, the olefin polymerization catalyst for polyolefin polymerization containing Formula A may have excellent properties in controlling the molecular weight and copolymerization of the polyolefin. In addition, when the bridge substituent between the cyclopentadiene groups in the transition metal compound of the formula (A) is a cyclobutyl group (Cyclobutyl), the activity and polymerization of the olefin polymerization catalyst compared to the case where the bridge substituent is an alkyl (alkyl) It has excellent performance characteristics.

On the other hand, the olefin polymerization catalyst for polyolefin polymerization according to an embodiment of the present invention may include at least one of the transition metal compounds illustrated above and a cocatalyst compound.

The cocatalyst compound may include one or more of a compound represented by the following formula (I), a compound represented by the formula (II), and a compound represented by the formula (III).

<Formula Ⅰ>

In Formula (I), n is an integer of 2 or more, and R _a may be a halogen atom, a C _1-20 hydrocarbon group, or a C _1-20 hydrocarbon group substituted with halogen. Specifically, R _a may be methyl, ethyl, n-butyl or isobutyl, but is not limited thereto.

<Formula Ⅱ>

In Formula II, D is aluminum (Al) or boron (B), and Rb, Rc, and Rd are each independently a halogen atom, a C _1-20 hydrocarbon group, or a C _1-20 hydrocarbon group substituted with halogen, or C _{1- It} may be a ₂₀ alkoxy group. Specifically, when D is aluminum, Rb, Rc and Rd may each independently be methyl or isobutyl, and when D is boron, Rb, Rc and Rd may each be pentafluorophenyl, but It is not limited.

<Formula Ⅲ>

^{[LH] + [Z (A} ) 4] - or ^{[L] + [Z (A} ) 4] -

In the formula (III), L is a neutral or cationic Lewis base, [LH] ⁺ or [L] ⁺ is Brønsted acid, Z is a group 13 element, and A is each independently substituted or unsubstituted C _{6- It may be a 20} aryl group or a substituted or unsubstituted C _1-20 alkyl group. Specifically, the [LH] ⁺ may be a dimethylanilinium cation dimethyl, wherein [Z (A) _4] ^- is _{[B (C 6 F 5)} 4] - can be a, the [L] ⁺ is [( C ₆ H ₅ ) ₃ C] ⁺ , but is not limited thereto.

The olefin polymerization catalyst may further include a carrier.

The carrier is not particularly limited as long as it can support a transition metal compound for an olefin polymerization catalyst and a cocatalyst compound. In an exemplary embodiment, the carrier can be carbon, silica, alumina, zeolite, magnesium chloride, and the like.

As a method of supporting the transition metal compound for the olefin polymerization catalyst and the cocatalyst compound on a carrier, a physical adsorption method or a chemical adsorption method can be used.

In an exemplary embodiment, the physical adsorption method is a method in which a solution in which a transition metal compound for an olefin polymerization catalyst is dissolved is contacted with a carrier and then dried, and a solution in which a transition metal compound for an olefin polymerization catalyst and a cocatalyst compound is dissolved is contacted with a carrier. After drying, a method in which a transition metal compound for an olefin polymerization catalyst is dissolved is contacted with a carrier, followed by drying and preparing a carrier carrying a transition metal compound for an olefin polymerization catalyst, and separately, a solution in which the cocatalyst compound is dissolved After contact with the carrier and dried to prepare a carrier carrying the cocatalyst compound, it may be a method of mixing them.

In an exemplary embodiment, the chemical adsorption method is a method in which a cocatalyst compound is first supported on a surface of a carrier, and then a transition metal compound for an olefin polymerization catalyst is supported on a cocatalyst compound, or a functional group on the surface of the carrier (for example, In the case of silica, it may be a method of covalently bonding a hydroxy group (-OH) on the silica surface with a catalyst compound.

The sum of the supported amounts of the main catalyst compound containing the transition metal compound may be 0.001 mmol to 1 mmol based on 1 g of the carrier, and the supported amount of the cocatalyst compound may be 2 mmol to 15 mmol on the basis of 1 g of the carrier.

However, such a carrier is not necessarily included, and its use can be appropriately selected as necessary.

The olefin polymerization catalyst comprising the transition metal compound of the present invention has stability at high temperature and has excellent reactivity with olefins, particularly α-olefins, so it is easy to polymerize olefins, has high catalytic activity, and has low molecular weight and low viscosity. It is possible to manufacture polyolefins having properties.

This is particularly the case where two adjacent R ⁷ to R ¹⁰ of the transition metal compound of the present invention are connected to each other to form a substituted or unsubstituted aromatic C ₆ ring, which is relatively rich in electrons, thereby improving the (co)polymerization reactivity of olefins It may be due to, but is not limited to.

Hereinafter, specific production examples of the compounds represented by the formulas A to D among the transition metal compounds for the olefin polymerization catalyst of the present invention will be described.

<Production Example 1> Preparation of a compound of formula (A)

Preparation Example 1-1: Preparation of 1,1'-binaphthyl-2,2'-dicarboxylic acid

To a solution of 2,2'-dibromo-1,1'-binaphthyl (3.85 g, 9.34 mmol) diluted in THF (40 mL), t-BuLi (15.8 g, 41.1 mmol, 1.7 M in pentane) was added at -78°C. After the addition, the mixture was stirred for 1 hour. CO2 gas was injected at -78°C for 3 minutes, and then the temperature was gradually raised to room temperature and stirred for 12 hours. After the reaction was terminated by adding 10% HCl at 0°C, THF was removed under vacuum. The organic layer was separated by extraction with ethyl acetate, and recrystallized with chloroform to obtain 3.49 g (quant.) of 2,2'-dibromo-1,1'-binaphthyl, a white solid compound having the following 1H-NMR spectrum.

1H-NMR (DMSO-d6, 300 MHz): δ 12.4 (s, 2H), 8.11-8.00 (m, 6H), 7.54 (t, 2H), 7.27 (t, 2H), 6.87 (d, 2H).

Preparation Example 1-2: Preparation of 7H-dibenzo[c,g]fluoren-7-one

1,1'-binaphthyl-2,2'-dicarboxylic acid (3.02 g, 8.82 mmol) prepared in Preparation Example 1-1 and acetic anhydride (30 mL) were mixed and stirred at 140°C for 1 hour 30 minutes. . After removing acetic anhydride under vacuum, the remaining reaction solution was stirred at 300°C for 3 hours. After filtering with dichloromethane, 7H-dibenzo[c,g]fluoren-7-one 1.17 as a red solid compound having the following 1H-NMR spectrum through column chromatography (hexane: dichloromethane = 1: 1, v/v) g (47%).

1H-NMR (CDCl3, 300 MHz): δ 8.37-8.33 (m, 2H), 7.92-7.87 (m, 2H), 7.83 (d, 2H), 7.77 (d, 2H), 7.60-7.55 (m, 4H ).

Preparation Example 1-3: Preparation of 7H-dibenzo[c,g]fluorene

7H-dibenzo[c,g]fluoren-7-one (641 mg, 2.29 mmol), N2H4·H2O (2.86 g, 57.2 mmol) and KOH (385 mg, 6.86 mmol) prepared in 1-2 were prepared in the above preparation. The solution dispersed in diethylene glycol (30 mL) was stirred at 170° C. for 3 hours. The reaction was terminated by adding 10% HCl at 0° C. and the resulting solid was filtered. It was dried under vacuum to obtain 603 mg (99%) of 7H-dibenzo[c,g]fluorene, a dark brown solid compound having the following 1H-NMR spectrum.

1H-NMR (CDCl3, 300 MHz): δ 8.73 (d, 2H), 7.97 (d, 2H), 7.86 (d, 2H), 7.73 (d, 2H), 7.59-7.48 (m, 4H), 4.13 ( s, 2H).

Preparation Example 1-4: Preparation of (7H-dibenzo[c,g]fluorene) lithium

7-dibenzo[c,g]fluorene (585 mg, 2.20 mmol) prepared in Preparation Example 1-3 was diluted in diethyl ether (50 mL) in n-BuLi (980 mg, 2.30 mmol, 1.6 M in Hexane) was slowly added at -30 °C, and the temperature was gradually raised to room temperature and stirred for 12 hours. The resulting solid was filtered and dried under vacuum to obtain 598 mg (100%) lithium (7H-dibenzo[c,g]fluorene), an ocher solid compound.

Preparation Example 1-5: Preparation of 9-[1-(2,4-Cyclopentadien-1-yl)-1-cyclobutyl]-7H-dibenzo[c,g] fluorene

5-cyclobutylidene-1,3-cyclopentadiene in a solution in which (7H-dibenzo[c,g]fluorene) lithium (596 mg, 2.19 mmol) prepared in Preparation Example 1-4 was dispersed in diethyl ether (35 mL). 518 mg, 4.38 mmol) was slowly added to a solution diluted in diethyl ether (10 mL) at -30 °C, and the temperature was gradually raised to room temperature and stirred for 3 days. After completion of the reaction, the organic layer was separated by extraction with diethyl ether and aqueous NH4Cl. Recrystallized with Hexane, 9-[1-(2,4-Cyclopentadien-1-yl)-1-cyclobutyl]-7H-dibenzo[c,g] fluorene 654 mg, a white solid compound having the following 1H-NMR spectrum (78%).

1H-NMR (CDCl3, 300 MHz): δ 8.56-8.47 (m, 2H), 7.95-7.89 (m, 2H), 7.79-7.76 (m, 4H), 7.50-7.44 (m, 4H), 5.96-5.81 (m, 1H), 5.74-5.67 (m, 1H), 5.59-5.50 (m, 1H), 4.42 (d, 1H), 2.99-2.79 (m, 2H), 2.58-2.44 (m, 2H), 2.39 -2.02 (m, 2H), 2.01-1.94 (m, 2H).

Preparation Example 1-6: Preparation of Cyclobutylidene [(cyclopentadienyl)-(7H-dibenzo[c,g]fluorenyl)] dilithium

9-[1-(2,4-Cyclopentadien-1-yl)-1-cyclobutyl]-7H-dibenzo[c,g] fluorene (319 mg, 0.83 mmol) prepared in Preparation Example 1-5 was diethyl ether To the solution diluted in (35 mL), n-BuLi (741 mg, 1.74 mmol, 1.6 M in Hexane) was slowly added at -30 °C, and the temperature was gradually raised to room temperature and stirred for 12 hours. The resulting solid was filtered and dried under vacuum to obtain Cyclobutylidene [(cyclopentadienyl)-(7H-dibenzo[c,g]fluorenyl)] dilithium 368 mg (quant., ether adduct), an ocher solid compound.

Preparation Example 1-7: Preparation of Cyclobutylidene [(cyclopentadienyl)-(7H-dibenzo[c,g]fluorenyl)] hafnium dichloride

Cyclobutylidene [(cyclopentadienyl)-(7H-dibenzo[c,g]fluorenyl)] dilithium (342 mg, 0.86 mmol) prepared in Preparation Example 1-6 was dissolved in toluene (40 mL) in HfCl4 (277 mg). , 0.86 mmol) was slowly added to a solution of toluene (5 mL) at -30 °C, and the temperature was gradually raised to room temperature and stirred for 12 hours. After completion of the reaction, it was extracted with toluene and filtered. After removing toluene under vacuum, washed with hexane to give Cyclobutylidene [(cyclopentadienyl)-(7H-dibenzo[c,g]fluorenyl)] hafnium dichloride 335 mg (61%) as a yellow solid compound having the following 1H-NMR spectrum. Got.

1H-NMR (C6D6, 300 MHz): δ 9.10 (d, 2H), 7.69 (d, 2H), 7.39-7.24 (m, 8H), 6.02 (t, 2H), 5.44 (t, 2H), 2.90- 2.77 (m, 2H), 2.58 (t, 2H), 2.26-2.14 (m, 1H), 1.88-1.74 (m, 1H).

Preparation Example 1-8: Preparation of Cyclobutylidene [(cyclopentadienyl)-(7H-dibenzo[c,g]fluorenyl)] hafnium dimethyl

MeMgBr (448 in Cyclobutylidene [(cyclopentadienyl)-(7H-dibenzo[c,g]fluorenyl)] hafnium dichloride (273 mg, 0.43 mmol) prepared in Preparation Example 1-7 was dispersed in toluene (20 mL). A solution diluted in mg, 1.30 mmol, 3.0 M in diethyl ether) in toluene (5 mL) was slowly added at -30 °C and stirred for 4 hours while refluxing at 70 °C. After completion of the reaction, it was extracted with toluene and filtered. After removing toluene under vacuum, washing with hexane, Cyclobutylidene [(cyclopentadienyl)-(7H-dibenzo[c,g]fluorenyl)] hafnium dimethyl (compound of formula (A) below) having a 1H-NMR spectrum as shown below 182 mg (71%) were obtained.

1H-NMR (C6D6, 300 MHz): δ 9.22 (d, 2H), 7.73 (d, 2H), 7.46-7.22 (m, 8H), 6.03 (t, 2H), 5.40 (t, 2H), 2.90- 2.80 (m, 2H), 2.68-2.58 (m, 2H), 2.34-2.18 (m, 1H), 1.92-1.84 (m, 1H), -1.37 (s, 6H).

<Formula A>

<Production Example 2> Preparation of a compound of formula (B)

Preparation Example 2-1: Preparation of Cyclobutylidene [(cyclopentadienyl)-(7H-dibenzo[c,g]fluorenyl)] zirconium dichloride

Cyclobutylidene [(cyclopentadienyl)-(7H-dibenzo[c,g]fluorenyl)] dilithium (127 mg, 0.32 mmol) prepared in Preparation Example 1-6 was dissolved in toluene (10 mL) in ZrCl4 (74 mg). , 0.32 mmol) was slowly added at -30 °C and the solution dispersed in toluene (3 mL) was slowly raised to room temperature and stirred for 12 hours. After completion of the reaction, it was extracted with toluene and filtered. Cyclobutylidene [(cyclopentadienyl)-(7H-dibenzo[c,g]fluorenyl)] zirconium dichloride (compound of formula B below), which is an orange solid compound having the following 1H-NMR spectrum by washing with hexane after removing toluene under vacuum 128 mg (74%) were obtained.

1H-NMR (C6D6, 300 MHz): δ 9.15 (d, 2H), 7.72 (d, 2H), 7.42-7.30 (m, 8H), 6.11 (t, 2H), 5.52 (t, 2H), 2.92- 2.82 (m, 2H), 2.60 (t, 2H), 2.28-2.16 (m, 1H), 1.92-1.82 (m, 1H).

<Formula B>

<Production Example 3> Preparation of a compound of formula (C)

Preparation Example 3-1: Preparation of 2,2-[(cyclopentadienyl)-(7H-dibenzo[c,g]fluorenyl)] propane

6,6-dimethylfulvene (522 mg, 4.92) in a solution in which (7H-dibenzo[c,g]fluorene) lithium (893 mg, 3.28 mmol) prepared in Preparation Example 1-4 was dispersed in diethyl ether (35 mL). mmol) was diluted in diethyl ether (5 mL), and slowly added at -78 °C, then the temperature was gradually raised to room temperature and stirred for 12 hours. After completion of the reaction, the organic layer was separated by extraction with diethyl ether and aqueous NH4Cl. 2,2-[(cyclopentadienyl)-(7H-dibenzo[c,g]fluorenyl)] propane 907 mg (74, light yellow solid compound having the following 1H-NMR spectrum through column chromatography (hexane 100%)) %).

1H-NMR (CDCl3, 300 MHz): δ 8.61 (d, 2H), 7.91 (d, 2H), 7.74-7.66 (m, 2H), 7.52-7.46 (m, 4H), 7.41 (d, 1H), 7.32 (d, 1H), 7.00-6.64 (m, 1H), 6.57-6.45 (m, 1H), 6.16-5.87 (m, 1H), 4.33 (d, 1H), 3.24-3.08 (m, 2H), 1.08 (s, 3H), 1.07 (s, 3H).

Preparation Example 3-2: Preparation of Isopropylidene [(cyclopentadienyl)-(7H-dibenzo[c,g]fluorenyl)] dilithium

2,2-[(cyclopentadienyl)-(7H-dibenzo[c,g]fluorenyl)] propane (519 mg, 1.39 mmol) prepared in Preparation Example 3-1 was diluted with diethyl ether (10 mL). After slowly adding n-BuLi (1.24 mg, 2.93 mmol, 1.6 M in Hexane) at -30°C, the temperature was gradually raised to room temperature and stirred for 12 hours. The resulting solid was filtered and dried under vacuum to obtain Isopropylidene [(cyclopentadienyl)-(7H-dibenzo[c,g]fluorenyl)] dilithium 600 mg (quant., ether adduct), a yellow solid compound.

Preparation Example 3-3: Preparation of Isopropylidene [(cyclopentadienyl)-(7H-dibenzo[c,g]fluorenyl)] hafnium dichloride

Ifpropylidene [(cyclopentadienyl)-(7H-dibenzo[c,g]fluorenyl)] dilithium (566 mg, 1.47 mmol) prepared in Preparation Example 3-2 was dissolved in toluene (40 mL) in HfCl4 (472 mg). , 1.47 mmol) was slowly added to a solution of toluene (10 mL) at -30 °C, and the temperature was gradually raised to room temperature and stirred for 12 hours. After completion of the reaction, it was extracted with toluene and filtered. After removing toluene under vacuum, washing with hexane gave Isopropylidene [(cyclopentadienyl)-(7H-dibenzo[c,g]fluorenyl)] hafnium dichloride 549 mg (60%) as a yellow solid compound having the following 1H-NMR spectrum. Got.

1H-NMR (CDCl3, 300 MHz): δ 8.84 (d, 2H), 7.95 (d, 2H), 7.88-7.82 (m, 2H), 7.61-7.54 (m, 4H), 7.49 (d, 2H), 6.30 (t, 2H), 5.88 (t, 2H), 2.48 (s, 6H).

Preparation Example 3-4: Preparation of Isopropylidene [(cyclopentadienyl)-(7H-dibenzo[c,g]fluorenyl)] hafnium dimethyl

MeMgBr (468) was added to a solution of Isopropylidene [(cyclopentadienyl)-(7H-dibenzo[c,g]fluorenyl)] hafnium dichloride (400 mg, 0.65 mmol) prepared in Preparation Example 3-3 in toluene (20 mL). A solution diluted in mg, 1.36 mmol, 3.0 M in diethyl ether) in toluene (2 mL) was slowly added at -30 °C and stirred for 2 hours while refluxing at 70 °C. After completion of the reaction, it was extracted with toluene and filtered. Isopropylidene [(cyclopentadienyl)-(7H-dibenzo[c,g]fluorenyl)] hafnium dimethyl (compound of formula C below), which is a yellow solid compound having the following 1H-NMR spectrum by washing with hexane after removing toluene under vacuum 241 mg (64%) was obtained.

1H-NMR (CDCl3, 300 MHz): δ 8.92 (d, 2H), 7.84 (t, 4H), 7.60-7.46 (m, 4H), 7.41 (d, 2H), 6.23 (t, 2H), 5.66 ( t, 2H), 2.26 (s, 6H), -1.82 (s, 6H).

<Formula C>

<Production Example 4> Preparation of a compound of formula (D)

Preparation Example 4-1: Preparation of Isopropylidene [(cyclopentadienyl)-(7H-dibenzo[c,g]fluorenyl)] zirconium dichloride

ZrCl4 (107 mg) in a solution in which Isopropylidene [(cyclopentadienyl)-(7H-dibenzo[c,g]fluorenyl)] dilithium (176 mg, 0.46 mmol) prepared in Preparation Example 3-2 was dispersed in toluene (20 mL). , 0.46 mmol) was slowly added to a solution of toluene (5 mL) at -30 °C, and the temperature was gradually raised to room temperature and stirred for 12 hours. After completion of the reaction, it was extracted with toluene and filtered. Isopropylidene [(cyclopentadienyl)-(7H-dibenzo[c,g]fluorenyl)] zirconium dichloride (compound of formula D below), which is a red-brown solid compound having the following 1H-NMR spectrum by washing with hexane after removing toluene under vacuum 107 mg (44%) were obtained.

1H-NMR (CDCl3, 300 MHz): δ 8.87 (d, 2H), 7.95-7.84 (m, 4H), 7.62-7.50 (m, 6H), 6.37 (t, 2H), 5.94 (t, 2H), 2.48 (s, 6 H).

<Formula D>

Polyolefin polymerization example (preparation of ethylene/1-octene copolymer)

<Example 1> Synthesis of ethylene and 1-octene copolymer using olefin polymerization catalyst comprising compound of formula A (1)

Ethylene and 1-octene were copolymerized as follows using an olefin polymerization catalyst including the compound of Formula A prepared in Preparation Example 1.

First, after heating the reactor of 850 mL to 140 ℃ to 150 ℃ using a jacket for temperature control, hexane (hexane) solvent, 1-octene (1-Octene, C ₈ ), hydrogen, scavenger and ethylene (Ethylene) , C ₂ ) while continuously maintaining the pressure of the reactor at 90 bar. The catalyst and the cocatalyst were continuously injected directly into the reactor, and in the case of the cocatalyst, dimethylaniliniumtetrakis(pentafluorophenyl)borate was used, and in the case of the scavenger, tri-iso-butylaluminium , TiBA).

In the case of the catalyst, an olefin polymerization catalyst containing the compound of formula A prepared in Preparation Example 1 was used, and the catalyst was dissolved in a certain amount of the compound of formula A in a hexane solvent and treated with triisobutylaluminum (TiBA), It was injected directly into the reactor.

The polymer melted in the reactor passes through the reactor discharge stream, enters the separator, separates unreacted ethylene and 1-octene from a hexane solvent, and then drying them in a vacuum oven at 80° C. for 12 hours or more [ethylene]-[1 -Octene] Polyolefin was prepared.

In the above manufacturing process, ethylene as an olefinic monomer was injected at a flow rate of 8.3 g/min, and comonomer 1-octene at a flow rate of 8 g/min, and formula A of Preparation Example 1 was 0.044 g/min as an olefin polymerization catalyst. Hydrogen (H ₂ ) was introduced at a flow rate of 0.2 g/hr to prepare a polyolefin, and the polyolefin thus prepared is hereinafter referred to as'Example 1'.

<Example 2> Synthesis of ethylene and 1-octene copolymer using olefin polymerization catalyst comprising compound of Formula A (2)

In Example 1, except for injecting 1-octene as a comonomer at a flow rate of 12 g/min, a polyolefin was prepared in the same manner, and the polyolefin thus prepared is hereinafter referred to as'Example 2'.

<Comparative Example 1> Synthesis of ethylene and 1-hexene copolymer using olefin polymerization catalyst comprising compound of formula E (1)

Ethylene and 1-hexene were copolymerized as follows using an olefin polymerization catalyst including a compound of Formula E.

<Formula E>

In Example 1, the transition metal compound of Formula E is injected at a flow rate of 0.049 g/min as an olefin polymerization catalyst, 10 g/min of 1-octene as a comonomer, and 0 g/hr of hydrogen (H ₂ ). A polyolefin was prepared in the same manner, except that it was injected at a flow rate of, and the polyolefin thus prepared is hereinafter referred to as'Comparative Example 1'.

<Comparative Example 2> Synthesis of ethylene and 1-hexene copolymer using an olefin polymerization catalyst containing a compound of Formula E (2)

In Comparative Example 1, a polyolefin was prepared in the same manner, except that 1-octene was injected as a comonomer at a flow rate of 12 g/min, and the polyolefin thus prepared is hereinafter referred to as'Comparative Example 2'.

<Comparative Example 3> Synthesis of ethylene and 1-hexene copolymer using olefin polymerization catalyst containing compound of formula E (3)

In Comparative Example 1, except for injecting 1-octene as a comonomer at a flow rate of 8 g/min and hydrogen (H ₂ ) at a flow rate of 0.3 g/hr, a polyolefin was prepared in the same manner, and the polyolefin thus prepared Is hereinafter referred to as'Comparative Example 3'.

<Comparative Example 4> Synthesis of ethylene and 1-hexene copolymer using olefin polymerization catalyst containing compound of formula E (4)

In Comparative Example 3, a polyolefin was prepared in the same manner, except that 1-octene was injected as a comonomer at a flow rate of 12 g/min, and the polyolefin thus prepared is hereinafter referred to as'Comparative Example 4'.

<Experimental Example>

The physical properties of the polyolefins prepared in Examples 1, 2 and Comparative Examples 1 to 4 and the catalytic activity of Formulas A and E were measured, and the results are shown in Table 1 below. In Table 1, in each of Examples and Comparative Examples, the density was measured at room temperature, the molecular weight (3D-GPC) at 160°C, and the Brookfield viscosity (Brookfield, cP) at 177°C.

	Example 1	Example 2	Comparative Example 1	Comparative Example 2	Comparative Example 3	Comparative Example 4
Catalyst type	Formula A		Formula E
Catalyst (g/min)	0.044	0.044	0.049	0.049	0.049	0.049
Ethylene (C2, g/min)	8.3	8.3	8.3	8.3	8.3	8.3
1-octene (C8, g/min)	8	12	10	12	8	12
C8/C2(Molar rate)	0.24	0.36	0.3	0.36	0.24	0.36
Catalytic activity (kg-PE/g-cat)	167	194	124	20.2	136	150
H 2 (g/hr)	0.2	0.2	0	0	0.3	0.3
Reaction temperature ( 0 C)	152	151	152	150	149	150
Density(g/cc)	0.880	0.863	0.863	0.868	0.875	0.858
Mn (3D-GPC)	8,077	6,519	71,450	100,416	25,279	30,456
MW (3D-GPC)	19,451	17,491	124,282	158,924	48,761	51,868
MWD (3D-GPC)	2.41	2.68	1.74	1.58	1.93	1.70
Viscosity (Brook field, cP at 177℃)	9,998	5,549	Measurement impossible	Measurement impossible	250,000	2,950,000

As shown in Table 1, in the case of Examples 1 and 2, the olefin polymerization catalyst containing the compound of Formula A has high catalytic activity, and the polyolefin polymerized under the catalyst has properties of low molecular weight and low viscosity. Able to know. On the other hand, in the case of Comparative Examples 1 to 4, it can be seen that the olefin polymerization catalyst containing the compound of Formula E has low catalytic activity, and the polyolefin polymerized under the catalyst has a high molecular weight.

In particular, comparing Examples 1 and 2 with Comparative Examples 3 and 4, despite having low hydrogen (H ₂ ) inputs in Examples 1 and 2, it was possible to produce low molecular weight polyolefins. In addition, the higher the amount of the injected catalyst tends to lower the molecular weight of the polymerized polyolefin, but in the case of Examples 1 and 2, even though a catalyst having a smaller amount than Comparative Examples 1 to 4 was used, the prepared polyolefin had a smaller molecular weight. It was found to have.

That is, the polyolefin according to an embodiment of the present invention has a high catalytic activity and is polymerized under an olefin polymerization catalyst including a transition metal compound having excellent molecular weight control and copolymerizability, and a low molecular weight and It can have low-viscosity properties.

In the above, embodiments belonging to the spirit of the invention have been described in detail with reference to the illustrated chemical structural formulas and manufacturing examples. However, the spirit of the invention is not limited to the illustrated chemical structural formulas and manufacturing examples, and the spirit of the invention may be variously modified based on the illustrated chemical structural formulas and manufacturing examples. The illustrated chemical structural formulas, manufacturing examples, and the like are provided to completely inform a person of ordinary skill in the art to which the invention pertains, and the scope of the spirit of the invention is defined in the scope of the claims. It is only defined by. Therefore, it should be understood that the embodiments described above are illustrative in all respects and not restrictive.

Claims (19)

1. A polyolefin having an olefinic monomer and a comonomer copolymerized under an olefin polymerization catalyst containing a transition metal compound for an olefin polymerization catalyst represented by the following Chemical Formula 1, and having a weight average molecular weight (Mw) of 20,000 or less.

   <Formula 1>

   

   (In the formula 1,

   M is titanium (Ti), zirconium (Zr) or hafnium (Hf),

   X is each independently halogen, C _1-20 alkyl, C _2-20 alkenyl, C _2-20 alkynyl, C _6-20 aryl, C _1-20 alkyl C _6-20 aryl, C _6-20 aryl C _1-20 alkyl, C _1-20 alkylamido, C _6-20 arylamido or C _1-20 alkylidene,

   R ¹ to R ⁴ are each independently hydrogen, C _1-20 alkyl, C _2-20 alkenyl, C _2-20 alkynyl, C _6-20 aryl, C _1-20 alkyl C _6-20 aryl, C _{6 -20} aryl C _1-20 alkyl, C _1-20 alkylamido, C _6-20 arylamido or C _1-20 alkylidene,

   R ⁵ and R ⁶ are each independently C _1-20 alkyl, C _2-20 alkenyl, C _2-20 alkynyl, C _6-20 aryl, C _1-20 alkyl C _6-20 aryl, C _6-20 Aryl C _1-20 alkyl, C _1-20 alkylamido, C _6-20 arylamido or C _1-20 alkylidene, or linked to each other to form a substituted or unsubstituted C _4-20 ring,

   R ⁷ to R ¹⁰ are two adjacent ones connected to each other to form a substituted or unsubstituted C _4-20 ring)
2. According to claim 1,

   The polyolefin is a polyolefin having a viscosity measured at 177 ℃ range of 5000 cP to 10000 cP.
3. According to claim 2,

   The polyolefin has a number average molecular weight (Mn) of 10,000 or less,

   A polyolefin having a molecular weight distribution (MWD) defined in Equation 1 below in the range of 2 to 3.

   [Equation 1]

   Mw/Mn
4. According to claim 1,

   The olefin-based monomer is ethylene, and the co-monomer is 1-octene polyolefin.
5. According to claim 1,

   X is each independently halogen or C _1-20 alkyl,

   R ¹ , R ³ , and R ⁴ are each hydrogen,

   R ² is C _1-20 alkyl,

   R ⁵ and R ⁶ are each independently C _1-20 alkyl or C _6-20 aryl, or connected to each other to form a substituted or unsubstituted aliphatic C _4-20 ring,

   The R ⁷ to R ¹⁰ are polyolefins in which two neighboring groups are connected to each other to form a substituted or unsubstituted aromatic C _5-20 ring.
6. The method of claim 5,

   The R ⁵ and R ⁶ are each independently methyl (methyl), or a polyolefin that is connected to each other to form an aliphatic C ₄ ring.
7. The method of claim 5,

   The R ⁷ to R ¹⁰ are polyolefins in which two neighboring groups are connected to each other to form a substituted or unsubstituted aromatic C ₆ .
8. According to claim 1,

   The Formula 1 is at least one of the following Formula 1-1 to Formula 1-12 polyolefin.

   <Formula 1-1>

   

   <Formula 1-2>

   

   <Formula 1-3>

   

   <Formula 1-4>

   

   <Formula 1-5>

   

   <Formula 1-6>

   

   <Formula 1-7>

   

   <Formula 1-8>

   

   <Formula 1-9>

   

   <Formula 1-10>

   

   <Formula 1-11>

   

   <Formula 1-12>

   

   (In the above formula 1-1 to formula 1-12,

   M is zirconium or hafnium,

   X are each independently halogen or C _1-20 alkyl)
9. The method of claim 8,

   The formula 1 is at least one of the following formula A to formula D polyolefin.

   <Formula A>

   

   <Formula B>

   

   <Formula C>

   

   <Formula D>

   
10. A method for producing a polyolefin, comprising forming a polyolefin by polymerizing an olefinic monomer and a comonomer under an olefin polymerization catalyst comprising a transition metal compound represented by the following Chemical Formula 1.

    <Formula 1>

    

    (In the formula 1,

    M is titanium (Ti), zirconium (Zr) or hafnium (Hf),

    X is each independently halogen, C _1-20 alkyl, C _2-20 alkenyl, C _2-20 alkynyl, C _6-20 aryl, C _1-20 alkyl C _6-20 aryl, C _6-20 aryl C _1-20 alkyl, C _1-20 alkylamido, C _6-20 arylamido or C _1-20 alkylidene,

    R ¹ to R ⁴ are each independently hydrogen, C _1-20 alkyl, C _2-20 alkenyl, C _2-20 alkynyl, C _6-20 aryl, C _1-20 alkyl C _6-20 aryl, C _{6 -20} aryl C _1-20 alkyl, C _1-20 alkylamido, C _6-20 arylamido or C _1-20 alkylidene,

    R ⁵ and R ⁶ are each independently C _1-20 alkyl, C _2-20 alkenyl, C _2-20 alkynyl, C _6-20 aryl, C _1-20 alkyl C _6-20 aryl, C _6-20 Aryl C _1-20 alkyl, C _1-20 alkylamido, C _6-20 arylamido or C _1-20 alkylidene, or linked to each other to form a substituted or unsubstituted C _4-20 ring,

    R ⁷ to R ¹⁰ are two adjacent ones connected to each other to form a substituted or unsubstituted C _4-20 ring)
11. The method of claim 10,

    The Chemical Formula 1 is a method for producing a polyolefin that is at least one of the following Chemical Formulas 1-1 to 1-12.

    <Formula 1-1>

    

    <Formula 1-2>

    

    <Formula 1-3>

    

    <Formula 1-4>

    

    <Formula 1-5>

    

    <Formula 1-6>

    

    <Formula 1-7>

    

    <Formula 1-8>

    

    <Formula 1-9>

    

    <Formula 1-10>

    

    <Formula 1-11>

    

    <Formula 1-12>

    

    (In the above formula 1-1 to formula 1-12,

    M is zirconium or hafnium,

    X are each independently halogen or C _1-20 alkyl)
12. The method of claim 11,

    The formula 1 is a method for producing a polyolefin of at least one of the following formula A to formula D.

    <Formula A>

    

    <Formula B>

    

    <Formula C>

    

    <Formula D>

    
13. The method of claim 12,

    The olefin polymerization catalyst has a catalytic activity of 160 kg-PE/g-Cat to 200 kg-PE/g-Cat.
14. The method of claim 10,

    The polyolefin is a method for producing a polyolefin having a weight average molecular weight (Mw) of 20,000 or less.
15. The method of claim 14,

    The polyolefin has a viscosity measured at 177°C of 5000 cP to 10000 cP.
16. The method of claim 15,

    The polyolefin has a number average molecular weight (Mn) of 10,000 or less, and a molecular weight distribution (Molecular Weight Disribution, MWD) defined by the following Equation 1 has a range of 2-3.

    [Equation 1]

    Mw/Mn
17. The method of claim 10,

    The olefinic monomer is ethylene, and the comonomer is 1-octene.
18. The method of claim 10,

    The olefin polymerization catalyst is a method for producing a polyolefin further comprising a co-catalyst compound.
19. The method of claim 18,

    The co-catalyst compound is a method for producing a polyolefin comprising at least one of a compound represented by the following formula (I), a compound represented by the formula (II) and a compound represented by the formula (III).

    <Formula Ⅰ>

    

    (In Formula A, n is an integer of 2 or more,

    R _a is a halogen atom, a C _1-20 hydrocarbon group or a C _1-20 hydrocarbon group substituted with halogen)

    <Formula Ⅱ>

    

    (D in the formula B is aluminum (Al) or boron (B),

    R _b , R _c and R _d are each independently a halogen atom, a C _1-20 hydrocarbon group, a C _1-20 hydrocarbon group substituted with halogen, or a C _1-20 alkoxy group)

    <Formula Ⅲ>

    ^{[LH] + [Z (A} ) 4] - or ^{[L] + [Z (A} ) 4] -

    (In the formula C, L is a neutral or cationic Lewis base,

    [LH] ⁺ and [L] ⁺ are Brønsted acids

    Z is a group 13 element,

    A is each independently a substituted or unsubstituted C _6-20 aryl group or a substituted or unsubstituted C _1-20 alkyl group)